Hair dyeing composition

ABSTRACT

Provided is a hair dyeing composition, containing a first part containing (a) a nitrogen-containing compound expressed by the general formula (1) or a salt thereof and a second part containing a component (b) of an oxidizing agent, wherein a pH upon use is 7.5 to 12, 
                         
wherein n=1 or 2, R 1  and R 3  to R 5  represent H, a hydroxy group, and an alkyl group with C12 or less optionally having a substituent, R 2  represents a hydroxy group, —R or —OR, in which R means the same as R 1  to R 5 , and two or more of R 1  to R 5  may be taken together to form a 3 to 8 membered-ring optionally having a substituent.

FIELD OF THE INVENTION

The present invention relates to a hair dyeing composition that is atwo-part hair dye containing a specific nitrogen-containing compound,which gives less damage to the hair and irritation to the scalp duringand after treatment, and has excellent hair bleaching ability and hairdyeing ability.

BACKGROUND OF THE INVENTION

An oxidative hair dye composed of the first part containing an alkaliagent, a precursor, and a coupler and the second part containinghydrogen peroxide is preferable because gray hair can be more evenlydyed and in that a hair color is greatly changed, as compared to otherhair dyes, and thus has been widely used in general. This is derivedfrom characteristics that in an oxidative hair dyes, alkaline hydrogenperoxide decomposes melanin inside hair and a color of the hair can bethus bleached to be brightened. Particularly, in recent years, it hasbecome preferred that black and white hair is dyed without unevennesswith more bright colors and with bright and vivid color tone, and therehas been a tendency that higher bleaching ability is required.

In order to obtain higher bleaching ability, it is considered that analkali agent or an oxidizing agent is contained in a large amount, butthere is a possibility of causing problems such that, depending on itsamount, strong pungent odor is accompanied, hair damage proceeds, andirritation is given to scalp.

Accordingly, a method of containing a specific triazacyclononanecompound in hair dyes (Patent Document 1) and a method of containing aspecific cyclic amine compound in a hair dye (Patent Document 2) havebeen proposed. However, these methods are insufficient for obtaininghigh bleaching ability with less pungent odor and less hair damage.

-   [Patent Document 1] JP-A-2002-255763-   [Patent Document 2] WO Publication No. 2003/051322

SUMMARY OF THE INVENTION

The present invention is to provide a hair dyeing composition,containing a first part containing a component (a) and a second partcontaining a component (b), wherein a pH upon use is 7.5 to 12:

(a) a nitrogen-containing compound expressed by the following generalformula (1) or a salt thereof:

wherein n denotes an integer of 1 or 2,

each of R¹ and R³ to R⁵ independently represents a hydrogen atom, ahydroxy group; or an alkyl group, an alkenyl group, an alkynyl group, acyclic hydrocarbon group, an aralkyl group or a cyanated alkyl groupeach having 12 or less carbon atoms; or a 5 to 7 membered-ring saturatedor unsaturated heterocyclic group,

two of R² may be the same or different, and each represents a hydroxygroup, —R or —OR, wherein R represents an alkyl group, an alkenyl group,an alkynyl group, a cyclic hydrocarbon group, an aralkyl group or acyanated alkyl group each having 12 or less carbon atoms, or a 5 to 7membered-ring saturated or unsaturated heterocyclic group,

these R¹ to R⁵ may have one or more of substituents selected from ahydroxy group, an amino group; and an alkyl group, a cyclic hydrocarbongroup, an aralkyl group, a heteroaryl group, an alkoxy group, an estergroup, and a cyanated alkyl group each having 8 or less carbon atoms,

two or more of R¹ to R⁵ may be taken together to form a saturated or anunsaturated 3 to 8 membered-ring, and the ring may have a substituentselected from a hydroxy group, and an alkyl group and a cyclichydrocarbon group which have 12 or less carbon atoms and optionally mayhave a substituent; and

(b) an oxidizing agent.

MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a hair dyeing composition excellent inhair bleaching ability and having less hair damage.

The present inventors found that, by containing a nitrogen-containingcompound having a specific structure or a salt thereof in a hair dyeingcomposition, an alkali agent and an oxidizing agent can be efficientlyworked inside hair and bleaching ability and hair dyeing ability can bethus improved, or amounts of the alkali agent and the oxidizing agentcan be reduced without lowering the bleaching ability and hair dyeingability, and hair damage and irritation to the scalp can be reduced.

In the present invention, a “hair dye” includes hair bleaches withoutcontaining dyes in addition to hair coloring agents containing dyes.Further, “dyeing the hair” means dyeing the hair as well as bleachingthe hair in a hair dye containing a dye, and means bleaching the hair ina bleach without containing a dye. The hair dye of the present inventionforms a two-part type composed of the first part containing an alkaliagent and the second part containing an oxidizing agent, and the “wholecomposition” in the present invention refers to the whole of compositionimmediately before using the mixture of the first part and the secondpart.

In a nitrogen-containing compound represented by the general formula (1)(hereinafter, referred to as a nitrogen-containing compound (1)) of acomponent (a) used in the present invention, examples of a saturated orunsaturated 3 to 8 membered-ring which is formed by taking a pluralityof substituents together include a pyrrolidine ring, a piperidine ring,a cyclohexane ring, a cyclopropane ring, and a pyrrole ring. As acombination of substituents taking together to form such a ring, acombination of R³ and R⁴ and a combination of two of R² are preferable,and a combination of R³ and R⁴ is more preferable.

In Rs in R¹, R³ to R⁵ and R², examples of the alkyl group having 12 orless carbon atoms include a methyl group, an ethyl group, a propylgroup, an isopropyl group, an n-butyl group, a sec-butyl group, and atert-butyl group; examples of the alkenyl group having 12 or less carbonatoms include an aryl group, a 2-propenyl group, a 3-methyl-2-butenylgroup, and a 3-butenyl group; examples of the alkynyl group having 12 orless carbon atoms include an ethynyl group, 2-propynyl group, 2-butenylgroup, and 3-butynyl group; examples of the cyclic hydrocarbon grouphaving 12 or less carbon atoms include a cyclopropyl group, acyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group,and a xylyl group; examples of the aralkyl group having 12 or lesscarbon atoms include a benzyl group, an α-methylbenzyl group, and aphenethyl group; and examples of the cyanated alkyl group having 12 orless carbon atoms include a cyanated methyl group, a 2-cyanated ethylgroup, and 3-cyanated propyl group. Further, examples of the 5 to 7membered-ring saturated or unsaturated heterocyclic group include apyrrolidinyl group, piperidyl group, a furyl group, a pyridyl group, anda morpholyl group.

Examples of the —OR group in R² include a methoxy group, an ethoxygroup, a propoxy group, an isopropoxy group, a cyclohexyloxy group, acyclopentyloxy group, a benzyloxy group, and a phenoxy group.

These R¹ to R⁵ may further have substituents, and examples of suchsubstituents include a hydroxy group, an amino group and an alkyl group,a cyclic hydrocarbon group, an aralkyl group, a heteroaryl group, alkoxygroup, an ester group, a mono- or dialkylamino group and a cyanatedalkyl group each having 8 or less of carbon atoms. Among these,preferable examples are a hydroxy group, a dimethylamino group, amethoxy group, an ethoxy group, a propoxy group, an isopropoxy group, aphenyl group, a tolyl group, and a cyclohexyl group. Note that “12 orless carbon atoms” in R¹ to R⁵ means the number including substituentswhich may be further contained therein.

As a substituent on a ring formed by taking two or more of R¹ to R⁵together, an alkyl group and a cyclic hydrocarbon group are preferable.Specifically, examples of the alkyl group include a methyl group, anethyl group, a propyl group, and an isopropyl group, an n-butyl group, asec-butyl group, a tert-butyl group, an n-pentyl group, a 2-ethylhexylgroup, and an n-hexyl group; examples of the cyclic hydrocarbon groupinclude a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, aphenyl group, a tolyl group, and a xylyl group.

In view of stability of a hair coloring agent in particular, thenitrogen-containing compound (1) is preferably a nitrogen-containingcompound in which, in the general formula (1), R¹ represents a hydrogenatom, or an alkyl group or a cyclic hydrocarbon group each having 12 orless carbon atoms, two of R² represent the same or different alkyl groupor cyclic hydrocarbon group each having 12 or less carbon atoms, R³ andR⁴ each independently represents a hydrogen atom, or an alkyl group or acyclic hydrocarbon group each having 12 or less carbon atoms, or bothare taken together to form a saturated 5 or 6 membered-ring containing anitrogen atom, and R⁵ represents a hydrogen atom, a hydroxy group, oralkyl group or a cyclic hydrocarbon group each having 12 or less carbonatoms.

Examples of a preferable nitrogen-containing compound (1) used in thepresent invention are shown in the following:

When the nitrogen-containing compound (1) has an asymmetric carbon atom,any of (S) form and (R) form, or a mixture of the both forms may beacceptable. A salt of the nitrogen-containing compound (1) preferablyincludes, for example, a salt with inorganic acids or organic acids suchas hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid,propionic acid, lactic acid, citric acid, succinic acid, hydrobromicacid, hydriodic acid, methane sulfonic acid, methyl sulfuric acid, andperchloric acid.

The nitrogen-containing compound (1) used in the present invention canbe produced by combining known reactions. For example, the compound (1)can be produced as follows.

An azethizine-2-carboxylic acid derivative or a proline derivative inwhich a carboxy group is esterified is used as a starting material, anda carbonyl group is alkylated using a Grignard reagent or the like, anda newly generated hydroxy group is then halogenated, thereafteraminating the resultant using an amine derivative to thereby cause aring expansion reaction at the same time when halogen is substituted,and thus the desired nitrogen-containing compound can be obtained.

Hereinafter, the production method of the nitrogen-containing compound(1) is shown in reaction schema 1, 2 and 3 with reference to an examplewhen the nitrogen-containing compound (1) is a pyrrolidine derivative(when n denotes 2 in the general formula (1)).

(in the formula R¹ and R⁶ represent hydrogen atoms, or alkyl groups orcyclic hydrocarbon groups each having 1 to 12 carbon atoms, and two ofR^(2a) may be the same or different, and represent alkyl groups orcyclic hydrocarbon groups each having 1 to 12 carbon atoms, R^(3a)represents an alkyl group or a cyclic hydrocarbon group each having 1 to12 carbon atoms, R^(4a) represents an alkyl group having 1 to 12 carbonatoms, R⁷ represents an alkylene group having 2 to 12 carbon atoms, R³and R⁴ represent hydrogen atoms, or alkyl groups or cyclic hydrocarbongroups each having 1 to 12 carbon atoms, or R³ and R⁴ are taken togetherwith the adjacent nitrogen atom to form a ring structure, R⁵ representsa hydrogen atom, a hydroxy group, or an alkyl group or a cyclichydrocarbon group each having 1 to 12 carbon atoms, and X¹, X², X³ andX⁴ represent halogen atoms.)

In the method shown in the reaction schema 1, a proline derivative (2)whose synthesis method has been known (JP-A-7-103098) is used as a rawmaterial, a 3-amino-2,2-dialkylpiperidine derivative (1a) in which R³and R⁴ are hydrogen atoms in the general formula (1) can be produced byundergoing the total four steps.

In the method shown in the reaction schema 2, a piperidine derivative(1a) obtained in the reaction schema 1 is used as a raw material, apiperidine derivative (1b) in which R³ is an alkyl group or a cyclichydrocarbon group each having 1 to 12 carbon atoms and R⁴ is a hydrogenatom in the general formula (1) can be produced by one step usingmonohaloalkane or a Leuckart reaction. Alternatively, using thepiperidine derivative (1a) obtained in the reaction schema 1 as a rawmaterial in the same manner, a piperidine derivative (1c) in which R³and R⁴ are taken together with the adjacent nitrogen atom to form acyclic structure in the general formula (1) can be produced in one stepusing dihaloalkane.

Also, in a method shown in the reaction schema 3, using halide (4) or(5) obtained in the reaction schema 1 as a raw material, a piperidinederivative (1d) in which R³ and R⁴ are hydrogen atoms, alkyl groups orcyclic hydrocarbon groups each having 1 to 12 carbon atoms, or are takentogether with the adjacent nitrogen atom to form a cyclic structure inthe general formula (1) can be produced by undergoing the aminationstep.

[Reaction Schema 1]

Dialkylation Step

A proline derivative (2) as a raw material whose synthesis method hasbeen known has at least one asymmetric carbon, and each asymmetriccarbon may be optically active or may be a racemic body. Alternatively,it may be a mixture with any ratio thereof.

Alkyl magnesium halide used in this step is expressed by R^(2a)MgX¹.R^(2a) corresponds to R² in the general formula (1), and the same groupsdescribed as specific examples of R² are included. Examples of a halogenatom expressed by X¹ include a chlorine atom, a bromine atom, and aniodine atom.

An amount of alkyl magnesium halide to be used is preferably in therange of 2 to 30 times by mole, and more preferably 3 to 5 times by molebased on the proline derivative (2) that is a raw material.

As a reaction solvent, a solvent generally used in an organic synthesisusing an organic metal compound, for example, ether solvents such asdiethyl ether, tetrahydrofuran, and dioxane, aromatic solvents such asbenzene, toluene and xylene, and halogen solvents such as chloroform anddichloromethane, hydrocarbon solvents such as heptane and hexane, ormixtures thereof can be used. Generally, diethyl ether, tetrahydrofuran,and toluene are preferable in view of handling.

A reaction temperature is preferably in the range of −20° C. to asolvent reflux temperature, and a reaction is performed under ordinarypressure, but if necessary, the reaction may be performed in apressurized condition or a reduced pressure condition.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,but these may be selected according to necessity, and it is possible toproceed to a next step without carrying out the purification step insome cases.

Halogenation Step

Examples of a halogenating agent used in this step include acid halidessuch as methane sulfonyl chloride, and p-toluene sulfonyl chloride, andthionyl chloride, phosphorus pentachloride, phosphorus trichloride, andphosphorus tribromide.

When an acid halide such as methane sulfonyl chloride and p-toluenesulfonyl chloride is used as a halogenating agent, it is preferable tosuitably combine and use organic amines such as triethylamine, pyridineand dimethylaminopyridine, and alkali agents such as inorganic alkalicompounds, for example, sodium hydroxide and potassium carbonate, and itis more preferable to combine and use organic amines.

An amount of a halogenating agent to be used is preferably in the rangeof 1 to 10 times by mole based on the prolinol derivative (3) that is araw material, and more preferably in the range of 1 to 2 times by mole.

When an acid halide such as methane sulfonyl chloride and p-toluenesulfonyl chloride is used as a halogenating agent, an amount of analkali agent to be combined upon use is in the range of 1 to 10 times bymole based on the prolinol derivative (3) that is a raw material, andmore preferably in the range of 1 to 2 times by mole.

Further, in this step, halogenation can be also performed by usingtriphenyl phenyl phosphine and tetrahalomethane such as carbontetrabromide in combination.

As a reaction solvent, although being different depending on ahalogenating agent to be used, solvents generally used in organicsynthesis, for example, alcohol solvents such as methanol, ethanol, and2-propanol, ether solvents such as diethyl ether, tetrahydrofuran, anddioxane, aromatic solvents such as benzene, toluene, and xylene, halogensolvents such as chloroform and dichloromethane, acetonitrile, DMF,DMSO, N-methyl pyrrolidone, and water, or a mixture thereof can be used.In general, dichloromethane, chloroform and toluene are preferable fromthe viewpoint of handling.

A reaction temperature is preferably in the range of −20° C. to asolvent reflux temperature, and more preferably in the range of −20° C.to a room temperature from the viewpoint of selectivity. The reaction iscarried out under ordinary pressure but may be preformed underpressurized condition or reduced pressure condition if necessary.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,and these may be selected according to necessity, and it is possible toproceed to a next step without carrying out the purification step insome cases.

Azidation Step

Examples of an azidating agent used in this step include an azide metalreagent such as sodium azide, and trimethylsilane azide. In general,sodium azide is preferable from the viewpoint of handling.

An amount of an azidating agent to be used is preferably in the range of1 to 20 times by mole based on 2-halo(dialkylmethyl)pyrrolidine (4) or3-halo-2,2-dialkyl piperidine (5), and more preferably in the range of 1to 3 times by mole.

As a reaction solvent, although being different depending on anazidating agent to be used, solvents generally used in organicsynthesis, for example, alcohol solvents such as methanol, ethanol, and2-propanol, ether solvents such as diethyl ether, tetrahydrofuran, anddioxane, aromatic solvents such as benzene, toluene, and xylene, halogensolvents such as chloroform and dichloromethane, acetonitrile, DMF,DMSO, N-methyl pyrrolidone, and water, or a mixture thereof can be used.In general, DMF and dichloromethane are preferable from the viewpoint ofhandling.

A reaction temperature is preferably in the range of −20° C. to asolvent reflux temperature. The reaction is carried out under ordinarypressure but may be preformed under pressurized condition or reducedpressure condition if necessary.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,and these may be selected according to necessity, and depending oncases, it is possible to proceed to a next step without carrying out thepurification step.

Reduction Step

This step can be performed by a hydrogenation reaction using a transfermetal catalyst. Examples of the transfer metal catalyst include Pd basedcatalysts such as Pd/C, Ru based catalysts such as Ru/C, Ru/Al₂O₃, andRuO₂, Rh based catalysts such as Rh/C and Rh/Al₂O₃, and Pt basedcatalysts such as Pt/C and PtO₂, and Ni based catalysts such as Raneynickel. Among these, Pd/C is preferable from the viewpoint of yield.These catalysts can be used alone or two or more kinds thereof can beused in combination.

An amount of a transfer metal catalyst to be used is preferably in therange of 0.05 to 50% by mass based on the azide product (7), and morepreferably in the range of 1 to 20% by mass from the viewpoint ofhandling.

As a reaction solvent, solvents generally used in organic synthesis, forexample, alcohol solvents such as methanol, ethanol, and 2-propanol,ether solvents such as diethyl ether, tetrahydrofuran, and dioxane,aromatic solvents such as benzene, toluene, and xylene, halogen solventssuch as chloroform and dichloromethane, acetonitrile, DMF, DMSO,N-methylpyrrolidone, and water, or mixture thereof can be used. Ingeneral, DMF and dichloromethane are preferable from the viewpoint ofhandling.

A hydrogenation reaction can be generally performed in the range of −20°C. to 250° C., preferably at a comparatively mild temperature, forinstance, at 20° C. to 120° C., more preferably at 20° C. to 80° C. Apressure during the hydrogenation reaction is generally at an ordinarypressure to 25 MPa, and preferably at an ordinary pressure to 15 MPa.

Further, in this step, reduction may be carried out also with ahydrogenation reagent such as lithium aluminum hydride (LiAlH₄) andsodium aluminum hydride (NaAlH₄).

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,and these may be selected according to necessity, and depending oncases, it is possible to proceed to a next step without carrying out thepurification step.

[Reaction Schema 2]

N-Alkylation Step (by Mono- or Dihaloalkane)

Examples of an alkylating agent in this step include monohaloalkanessuch as methane chloride, methane bromide, methane iodide, ethanebromide, n-propane chloride, n-propane bromide, isopropane bromide,n-butane bromide, t-butane bromide, n-hexane chloride, n-hexane bromide,n-hexane iodide, cyclohexane bromide, n-octane bromide, n-dodecanebromide, n-dodecane iodide, 2-bromoethanol, 6-bromohexanol, and2-chloroethyl methyl ether; and dihaloalkanes such as1,3-dichloropropane, 1,3-dibromopropane, 1,4-dichlorobutane,1,4-dibromobutane, 1,4-diiodobutane, 1,5-dibromopentane,1,4-dibromopentane, 1,6-dibromohexane, and 2,5-dibromohexane.

When monohaloalkane or dihaloalkane is used as an alkylating agent, itis preferable to add an alkali agent. Examples of the alkali agentinclude inorganic alkali compounds such as sodium hydrogen carbonate,sodium carbonate, potassium carbonate, calcium carbonate, cesiumcarbonate, sodium hydroxide, and potassium hydroxide; and organic aminecompounds such as triethylamine, pyridine, and N-methylmorpholine. Fromthe viewpoint of yield, inorganic alkali compounds such as sodiumhydrogen carbonate, sodium carbonate, and potassium carbonate arepreferable.

An amount of an alkylating agent to be used is preferably in the rangeof 1 to 30 times by mole, more preferably in the range of 1 to 10 timesby mole and even more preferably in the range of 1 to 5 times by molebased on 3-amino-2,2-dialkylpiperidine derivative (1a).

An amount of an alkali agent to be used differs depending on an alkaliagent to be used, but is preferably in the range of 1 to 30 times bymole, and more preferably 1 to 10 times by mole based on3-amino-2,2-dialkylpiperidine derivative (1a).

Alkylation can be achieved by performing reduction of an amide groupafter amidating an amino group in a 3-amino-2,2-dialkylpiperidinederivative (1a) with an acylating agent.

As a reaction solvent, although being different depending on analkylating agent and an alkali agent to be used, solvents generally usedin organic synthesis, for example, alcohol solvents such as methanol,ethanol, and 2-propanol, ether solvents such as diethyl ether,tetrahydrofuran, and dioxane, aromatic solvents such as benzene,toluene, and xylene, halogen solvents such as chloroform anddichloromethane, acetonitrile, DMF, DMSO, N-methylpyrrolidone, andwater, or a mixture thereof can be used. In general, toluene, chloroformand dichloromethane are preferable from the viewpoint of handling.

A reaction temperature is preferably in the range of −20° C. to asolvent reflux temperature, and a reaction is performed under ordinarypressure, but may be performed in a pressurized condition or a reducedpressure condition if necessary.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,but these may be selected according to necessity.

N-Alkylation Step (by Leuckart Reaction)

N-alkylation (in particular, N-methylation) in this step can beperformed by a Leuckart reaction using aldehydes such as formaldehydeand a reducing agent such as formic acid.

An amount of aldehyde to be used is in the range of to 30 times by mole,and more preferably in the range of 1 to 10 times by mole based on3-amino-2,2-dialkylpiperidine derivative (1a).

An amount of a reducing agent to be used is in the range of 1 to 30times by mole, and more preferably in the range of 1 to 10 times by molebased on 3-amino-2,2-dialkylpiperidine derivative (1a).

As a reaction solvent, although being different depending on analkylating agent and an alkali agent to be used, solvents generally usedin organic synthesis, for example, alcohol solvents such as methanol,ethanol, and 2-propanol, ether solvents such as diethyl ether,tetrahydrofuran, and dioxane, aromatic solvents such as benzene,toluene, and xylene, halogen solvents such as chloroform anddichloromethane, acetonitrile, DMF, DMSO, N-methylpyrrolidone, andwater, or a mixture thereof can be used. Alternatively, the reaction canbe carried out without a solvent in some cases. In general, water,ethanol and toluene are preferably used as a reaction solvent from theviewpoint of handling.

A reaction temperature is preferably in the range of −20° C. to asolvent reflux temperature, and the reaction is performed under ordinarypressure, but may be performed in a pressurized condition or a reducedpressure condition if necessary.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,but these may be selected according to necessity.

Reaction Schema 3: Amination Step

Amine used in this step is expressed by the following general formula(6):

(in the formula, R³ and R⁴ express the same meaning as the above.)

In the general formula (6), R³ and R⁴ preferably denote hydrogen atoms,alkyl groups having 1 to 4 carbon atoms, or pyrrolidine rings orpiperidine rings forming rings.

Specific examples of amine (6) used in this step include ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, t-butylamine, n-hexylamine,cyclohexylamine, n-octylamine, n-decylamine, n-dodecylamine, aniline,monoethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethylenediamine,dimethylamine, N-ethylmethylamine, diethylamine, diisopropylamine,diisobutylamine, dicyclohexylamine, bis(2-ethylhexyl)amine,didecylamine, diethanolamine, diisopropanolamine,N,N-dimethyl-N′-ethylethylenediamine, pyrrolidine, piperidine,hexamethyleneimine, 2-pyrrolidinemethanol, 2-piperidinemethanol,piperazine, and ethyl piperazine.

An amount of amine (6) to be used is preferably in the range of 1 to 30times by mole, and more preferably in the range of 1 to 10 times by molebased on 2-[halo(dialkylmethyl)pyrrolidine (4) or3-halo-2,2-dialkylpiperidine (5).

Further, in this step, depending on amine used as an aminating agent, itis preferable to add an alkali agent. Examples of the alkali agentinclude inorganic alkali compounds such as sodium hydrogen carbonate,sodium carbonate, potassium carbonate, calcium carbonate, cesiumcarbonate, sodium hydroxide, and potassium hydroxide, and organic aminecompounds such as triethylamine, pyridine, and N-methylmorpholine.

An amount of an alkali agent to be used is preferably in the range of 1to 30 times by mole, and more preferably in the range of 1 to 10 timesby mole based on 2-[halo (dialkylmethyl)pyrrolidine (4) or3-halo-2,2-dialkylpiperidine (5).

As a reaction solvent, solvents generally used in organic synthesis, forexample, alcohol solvents such as methanol, ethanol, and 2-propanol,ether solvents such as diethyl ether, tetrahydrofuran, and dioxane,aromatic solvents such as benzene, toluene, and xylene, halogen solventssuch as chloroform and dichloromethane, acetonitrile, DMF, DMSO,N-methylpyrrolidone, and water, or a mixture thereof can be used.Alternatively, the reaction can be carried out without a solvent in somecases. In general, chloroform, dichloromethane, and toluene arepreferable from the viewpoint of handling.

As a post treatment and a purification step after the reaction,filtration, extraction, drying, recrystallization, distillation underreduced pressure, column purification, and the like can be performed,and these may be selected according to necessity.

As described above, with reference to examples wherein anitrogen-containing compound (1) or a salt thereof is a pyrrolidinederivative (n=2 in the general formula (1)), production methods thereofhave been explained, and in the case where the nitrogen-containingcompound (1) or a salt thereof is a piperidine derivative (n=1 in thegeneral formula (1)), it can be also produced according to the abovedescribed methods.

The nitrogen-containing compound (1) or a salt thereof being a component(a) can be used in at least one kind, and a content thereof ispreferably 0.01 to 20% by weight in the whole composition, morepreferably 0.02 to 10% by weight, even more preferably 0.05 to 8% byweight, and even more preferably 0.1 to 5% by weight from the viewpointof sufficient bleaching and hair dyeing effect.

Examples of an oxidizing agent of the component (b) include hydrogenperoxide and hydrogen peroxide generating agents such as urea peroxide,melamine peroxide, sodium perborate, potassium perborate, sodiumpercarbonate, and potassium percarbonate, and among these, hydrogenperoxide is preferable. A content of an oxidizing agent is, as inhydrogen peroxide, preferably 0.1 to 12% by weight in the wholecomposition, more preferably 0.5 to 9% by weight, and even morepreferably 1 to 6% by weight from the viewpoints of sufficient bleachingand hair dyeing effect, and reduction of hair damage and scalpirritation.

If the hair dyeing composition of the present invention further containsone or more kinds of chelating agents whose use in a hair dyeingcomposition has been known, such as ethylenediamine tetraacetate,ethylenediamine hydroxyethyl triacetic acid and diethylenetriaminepentaacetic acid, or salts thereof as a component (c), it is preferablebecause an oxidizing agent and an alkali agent are efficiently reactedin hair. A content of these chelating agents is preferably in the rangeof 0.01 to 5% by weight in the whole composition from the viewpoint of asufficient bleaching and hair dyeing effect. These chelating agents canbe incorporated in one of the first part and the second part, or in theboth thereof.

The present invention can achieve more effective bleaching and dyeing byusing the component (a) with an alkali agent. Examples of an alkaliagent that can be used include ammonia, alkanolamines such asmonoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and2-aminobutanol, alkanediamine such as 1,3-propanediamine, carbonatesalts such as ammonium carbonate, ammonium hydrogen carbonate, guanidinecarbonate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogen carbonate. Among these, ammonia andalkanolamines are preferable, and among alkanolamines, monoethanolamineis more preferable. These alkali agents can be used alone or in two ormore kinds thereof in combination and contained in the first part. Thecontent thereof can be suitably selected within the range satisfyingnecessity of pH, and is preferably 0.05 to 10% by weight in the wholecomposition, more preferably 0.1 to 5% by weight, and even morepreferably 0.2 to 3% by weight from the viewpoints of a sufficientbleaching and hair dyeing effect and reduction of hair damage and scalpirritation.

When the composition of the present invention is a hair dye containing adye, an oxidative dye intermediate or a direct dye is contained in thefirst part as dye. When the composition of the present invention is ahair bleach, these dyes are not contained therein.

As an oxidative dye intermediate suitable for the hair dyeingcomposition of the present invention, known precursors and couplerswhich are generally used as a hair dye can be used.

Examples of the precursor include paraphenylenediamine,toluene-2,5-diamine, 2-chloroparaphenylenediamine, paraminophenol,paramethylaminophenol, ortho-aminophenol, 2,4-diaminophenol andN-phenylparaphenylenediamine, and salts thereof.

Examples of the coupler include metaphenylenediamine,2,4-diaminophenoxyethanol, metaminophenol, 2-methyl-5-aminophenol,2-methyl-5-(2-hydroxyethylamino)phenol, resorcin, 1-naphthol,1,5-dihydroxynaphthalene and hydroquinone, and salts thereof.

The precursors and couplers can be respectively used alone or in two ormore kinds thereof in combination, and the content thereof is eachpreferably 0.01 to 5% by weight, and more preferably 0.1 to 4% by weightof the whole composition.

On the other hand, as a direct dye, known acid dyes, basic dyes,disperse dyes, and reactive dyes which are available for a hair dye canbe used. Examples of the acid dyes include blue No. 1, violet No. 401,black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203,and acid orange 3. Examples of the basic dyes include basic blue 99,basic brown 16, basic brown 17, basic red 76, and basic yellow 57.Examples of the direct dyes except for acid dyes and basic dyes include2-nitroparaphenylenediamine, 2-amino-6-chloro-4-nitrophenol,3-nitroparahydroxyethylaminophenol, 4-nitro-ortho-phenylenediamine,4-amino-3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol,N,N-bis-(2-hydroxyethyl)-2-nitroparaphenylenediamine, disperse violet 1,disperse blue 1, disperse black 9, HC blue 2, HC orange 1, HC red 1, HCred 3, HC yellow 2, HC yellow 4, and HC yellow 5.

These direct dyes can be used alone or in combination of two or morekinds thereof, and the content thereof is preferably 0.001 to 5% byweight, and more preferably 0.01 to 4% by weight in the wholecomposition. Alternatively, an oxidative dye intermediate and a directdye can be used in combination, and in this case, a total amount of theoxidative dye intermediate and the direct dye is preferably 0.05 to 10%by weight, and more preferably 0.1 to 8% by weight in the wholecomposition.

The hair dyeing composition of the present invention can further containa conditioning component. The conditioning component may be those usedas cosmetics, and the hair dyeing composition contains soluble ordispersible polymers or oils. These conditioning components are attachedto hair when diluted with water at the time of hair conditioningtreatment or washing hair with shampoo after hair dyeing treatment,thereby a conditioning effect can be further improved.

Examples of preferable conditioning components used in the hair dyeingcomposition of the present invention include silicones, organicconditioning oils (e.g., hydrocarbon oil, polyolefin, aliphatic esters,and aliphatic amides), and a conditioning polymer. A content of theseconditioning components is preferably 0.01 to 20% by weight in the wholecomposition, more preferably 0.05 to 15% by weight, and even morepreferably 0.5 to 5% by weight.

Examples of the silicones are shown in the following. (Silicones-1)dimethicone, dimethiconol, cyclomethicone

Silicone expressed by the general formula (8) below is exemplified:

(in the formula, R¹⁰ denotes a methyl group or a hydroxy group, or twoof R¹⁰ may form one oxygen atom to constitute a ring, and a denotes anumber of 1 to 20,000.)

Examples thereof include BY11-026, BY22-19, and FZ-3125, which are allmade by Dow Corning Toray Co., Ltd. Further, higher polymerizeddimethylpolysiloxane can be used in a form of being dissolved ordispersed in a liquid oil (e.g., (i) lower polymerizeddimethylpolysiloxane, or (ii) liquid silicone oil such ascyclomethicone, or liquid hydrocarbon oil such as isoparaffin)

(Silicones-2) Amino-Modified Silicones

Various amino-modified silicones can be used, but in particular,amino-modified silicones expressed by the general formula (9) and havingan average molecular weight of about 3,000 to 100,000, which are knownas the INCI name of amodimethicone, are preferable.

(in the formula, R¹¹ denotes a methyl group or a hydroxy group, Xdenotes a bivalent hydrocarbon group having 2 to 6 carbon atoms, and band c denote numbers of 1 to 20,000.)

This amino-modified silicone is preferably used as an aqueous emulsionliquid, and examples of commercially available products thereof includeSM8704C (made by Dow Corning Toray Co., Ltd.) and DC 929 (made by DowCorning Co., Ltd.).

Examples of other amino-modified silicones include bis(C13-15 alkoxy)PGamodimethicone expressed by the following general formula (10), and as acommercially available product thereof, include 8500 Conditioning Agent(Dow Corning Co., Ltd.).

(in the formula, R¹² denotes a linear or branched chain alkyl grouphaving 13 to 15 carbon atoms, and 75% of Ys denote —CH₂CH(OH)CH₂OH groupand 25% denote hydrogen atoms.)

Furthermore, amino-modified silicone to be a copolymer containing apolyoxyalkylene block in a main chain can be also used, and an examplethereof includes bisisobutyl PEG-15/amodimethicone expressed by thegeneral formula (11).

(in the formula, R¹³ denotes an isobutylene group, d denotes a number oftwo or more, preferably a number of 2 to 1,000, e denotes a number ofone or more, preferably a number of 1 to 50, and f denotes a number oftwo or more, preferably a number of 2 to 100).

Examples of commercially available products thereof include FZ-3789 andsilicone SS-3588 (made by Dow Corning Toray Co., Ltd.).

(Silicones-3) Polyether-Modified Silicones

Various polyether-modified silicones can be used, but preferable arepolyether-modified silicones expressed by the general formula (12) andknown as the INCI name as PEG-n dimethicones having an average molecularweight of 3,000 to 100,000, in which a part of a methyl group indimethicone is substituted with polyethylene glycol (for example, PEG-3dimethicone, PEG-7 dimethicone, PEG-8 dimethicone, PEG-9 dimethicone,PEG-10 dimethicone, PEG-12 dimethicone, and PEG-14 dimethicone), andpolyether-modified silicones expressed by the general formula (13) andknown as the INCI name as polysilicone-13:

(in the formula, g and h denote numbers of 1 to 1,000, and i denotes anumber of 1 to 2,000),

(in the formula, j, k and l denote numbers of 1 to 1,000, and m denotesa number of 1 to 2,000.)(Silicones-4) Other Silicones

Examples of silicones other than the above includemethylphenylpolysiloxane, fatty acid-modified silicones,alcohol-modified silicones, alkoxy-modified silicones, epoxy-modifiedsilicones, fluorine-modified silicones, and alkyl-modified silicones.

In addition, such silicones being diluted or dispersed by volatilesilicone, involatile silicone and the like, and those forming dispersionliquid particles in an aqueous surfactant can be also used.

Further, organic conditioning oils are preferably liquids with lowviscosity and insoluble to water, and hydrocarbon oil, polyolefin,aliphatic esters, fatty acid amides, and a mixture thereof are included.In a measurement at 40° C., a viscosity of such an organic conditioningoil is preferably 1 to 200 mPa·s, more preferably 1 to 100 mPa·s, andeven more preferably 2 to 50 mPa·s.

Examples of aliphatic esters include esters having hydrocarbon chains,which are derived from a fatty acid and an alcohol (e.g., monoester,polyvalent alcohol ester, and di- and tricarboxylate ester). Ahydrocarbon group in these aliphatic esters may further have othercompatible functional moieties such as an amide group and an alkoxygroup (e.g., ethoxy or other bonding), or may covalently bind thereto.Specific examples of preferable aliphatic esters include isopropylmyristate and octyldecyl myristate.

Examples of aliphatic amides include amides having a hydrocarbon chain,which is derived from a fatty acid and alkylamine or alkanolamine. Ahydrocarbon group in these aliphatic amides may further have othercompatible functional moiety such as an amide group and an alkoxy group(e.g., ethoxy or other bonding), or may covalently bind thereto.Specific examples of preferable aliphatic amides include oleic aciddiethanolamide, lauric acid diethanolamide, palm fatty acid amide, andpalm fatty acid diethanolamide.

As a conditioning polymer, a cationic polymer is preferable, and canfurther contain anionic, nonionic and/or amphoteric polymer. Any anioniccounter ion of a cationic polymer may be used if the cationic polymer isin a state of being dissolved and the counter ion is physically andchemically compatible with an essential component of the hair dyeingcomposition, or as long as performance, stability or visual appearanceof a product is not damaged. Examples of such a counter ion includehalide ion (e.g., chloride ion, fluoride ion, bromide ion, and iodideion), sulfate ion, methyl sulfate ion and a mixture thereof. Examples ofcationic polymers include cationic polysaccharide (e.g., cationiccellulose derivative and cationic guar), a copolymer of a vinyl monomerhaving a protonated amine-substituent group or a quaternaryammonium-substituent group with an aqueous monomer, a vinylpyrrolidonecopolymer, and cationic protein.

The hair dyeing composition of the present invention can further containpolyalkylene glycol, and an amount thereof is 0.005 to 1.5% by weight inthe whole composition, preferably 0.025 to 1.2% by weight, morepreferably 0.05 to 1% by weight, and even more preferably 0.1 to 0.5% byweight. Such polyalkylene glycol is compatible with the components (A)to (C) of the present invention, and is required not to significantlydamage stability, visual appearance or performance of a product.Specific examples thereof include polyethylene glycol and polypropyleneglycol, and may be a mixture of the both or may be a copolymer thereofwith ethylene oxide and propylene oxide.

In the hair dyeing composition of the present invention, water and/or anorganic solvent is used as a medium. Examples of the organic solventinclude lower alkanols such as ethanol and 2-propanol, aromatic alcoholssuch as benzyl alcohol and benzyloxyethanol, polyols such as propyleneglycol, 1,3-butanediol, diethylene glycol, and glycerin, cellosolvessuch as ethyl cellosolve, butyl cellosolve, and benzyl cellosolve, andcarbitols such as ethyl carbitol and butyl carbitol.

The hair bleaching composition and the hair dyeing composition of thepresent invention can be added with other components generally used ascosmetics materials in addition to the above described components.

Examples of such an optional component include hydrocarbons, animal andvegetable fat and oils, higher fatty acids, permeation accelerators,cationic surfactants, natural or synthesized polymers, higher alcohols,ethers, amphoteric surfactants, nonionic surfactants, proteinderivatives, amino acids, antiseptic agents, chelating agents,stabilizers, antioxidants, vegetable extracts, crude drug extracts,vitamins, pigments, fragrant materials, and ultraviolet absorbers.

The hair dyeing composition of the present invention is provided as atwo-part type composed of the first part containing an alkali agent andthe second part containing an oxidizing agent in the same manner ascurrently widely used oxidation type hair bleaches or dyes. Formulationsof these first part and second part can be, for instance, liquid,emulsion, cream, gel, paste, mousse, and the like, and also can be aform of an aerosol.

A mixing ratio (weight ratio) of the first part and the second part ofthe hair dyeing composition of the present invention is preferably inthe range of 1:0.5 to 1:3 from the viewpoint of practicality.

In the hair dyeing composition of the present invention, it ispreferable that a pH (25° C.) of the first part is 8 to 12 and a pH (25°C.) of the second part is 2 to 5, and a pH after mixing the first partand the second part is 7.5 to 12, and it is preferable to be pH 8 to 11from the viewpoints of a bleaching and hair dyeing effect and skinirritating properties. Examples of a pH adjuster include inorganic acidssuch as hydrochloric acid and phosphoric acid, organic acids such ascitric acid, glycolic acid, and lactic acid, hydrochloride such asammonium chloride and monoethanolamine hydrochloride, phosphate such aspotassium dihydrogen phosphate and disodium hydrogen phosphate.

The hair dyeing composition of the present invention preferably has aviscosity such that liquid dripping hardly occurs when the first partand the second part are mixed and applied to the hair. Specifically, aviscosity measured using a B type rotation viscometer at 25° C. (rotorin use No. 3, 12 rpm, value after rotation for 1 minute) is preferably2,000 to 100,000 mPa·s.

In order to carry out dyeing treatment to the hair by using the hairdyeing composition of the present invention, for instance, the firstpart and the second part of the hair dyeing composition of the presentinvention are mixed and the mixture is then applied to the hair at atemperature of 15 to 45° C., and leaving for an action time of 1 to 60minutes, preferably 3 to 45 minutes, and the hair is washed and thendried.

EXAMPLES Production Example 1 3-amino-1,2,2-triethylpiperidine (compound1-II-13)

Dialkylation Step

A four-necked pear-shaped flask (3 L) was charged with 380 mL (1.14 mol)of a 3.0 M ethyl magnesium bromide/diethyl ether solution and stirredwhile cooling with ice in a nitrogen atmosphere. Then, a solution of65.05 g (0.38 mol) of 1-ethylproline ethyl ester and 600 mL of toluenewas dropped over about 1 hour so that the reaction solution was 15° C.or less. After completion of the dropping, the reaction solution washeated to 50° C. and stirred for 3 hours.

Thereto was added 600 g of a 10% aqueous ammonium chloride solution, andthe organic layer was separated, and the aqueous layer was then furtherextracted with diisopropyl ether (500 mL×3). The organic layer combinedwas dried over sodium sulfate anhydride, and then the solvent wasdistilled off under reduced pressure to thereby obtain a yellow liquid.The obtained liquid was purified by distillation at reduced pressure(133.33 Pa, 90° C.) and 52.96 g (yield of 75%) of a desired product, aprolinol derivative, was thus obtained as a colorless liquid.

Halogenating Step

A 20 L-kolben was charged with 1050 g (5.66 mol) of the above prolinolderivative, 857 g (8.49 mol) of triethylamine, and 12 L ofdichloromethane, and the mixture was stirred while cooling with ice in anitrogen atmosphere. Then, 748 g (6.50 mol) of methane sulfonyl chloridewas added dropwise. After completion of the dropping, the resultant wasstirred at 40° C. for one day.

While cooling with ice, 9.2 kg of water was added thereto and extractedwith dichloromethane (10 L×2). The organic layer combined was dried oversodium sulfate anhydride, and then the solvent was distilled off underreduced pressure to thereby obtain 820 g of a chloro product as amixture of a pyrrolidine derivative (general formula (4)): a piperidinederivative (general formula (5))=4:1.

This product was used in the following azidation step without furtherperforming purification.

Azidation Step

A kolben (20 L) was charged with 820 g (4.02 mol) of the above chloroproduct, 550 g (8.46 mol) of sodium azide and 12 L of DMF, and themixture was stirred at 40° C. for 4 hours.

The reaction solution was added to 9 kg of ice water and then extractedwith dichloromethane (12 L×3). The organic layer was dried over sodiumsulfate anhydride and then the solvent was distilled off under reducedpressure to thereby obtain 1076 g of a crude product. The resultantcrude product was purified by silica gel chromatography(dichloromethane:methanol=10:1), and 610 g of an azide product wasobtained as a reddish brown liquid.

Reduction Step

An autoclave reaction vessel (20 L) was charged with 605 g (2.87 mol) ofthe above azide product, 8 L of methanol, and 136 g of 10% Pd/C (wet),and the mixture was stirred for 4 hours with replacing at hydrogenpressure of 0.5 MPa every 30 minutes.

A catalyst was removed by filtration, and then the filtrate wasconcentrated to thereby obtain 461 g of a crude product as a paleyellowish brown liquid. The crude product was purified by distillationat reduced pressure (533 Pa, 70° C.), and 55.3 g of a desired product,3-amino-1,2,2-triethylpiperidine (compound 1-II-13, yield of 10%), wasobtained as a colorless transparent liquid.

¹H NMR (400 MHz, CDCl₃, ppm): σ 0.83-0.87 (3H), 0.88-0.92 (3H),0.95-0.99 (3H), 1.20 (2H), 1.32-1.84 (8H), 2.41-2.53 (3H), 2.57-2.63(1H), 2.71-2.74 (1H) ¹³C NMR (400 MHz, CDCl₃, ppm): σ 61.20, 51.50,45.00, 43.54, 29.02, 23.20, 22.36, 22.10, 15.66, 9.49, 7.82

Production Example 2 3-pyrrolidinyl-1,2,2-triethylpiperidine (compound1-II-12)

N-Alkylation Step

A four-necked pear-shaped flask (500 mL) was charged with 15.00 g (0.08mol) of 3-amino-1,2,2-triethylpiperidine obtained in Example 1, 35.00 g(0.16 mol) of 1,4-dibromobutane, 34.09 g (0.41 mol) of sodium hydrogencarbonate, and 150 mL of toluene, and the mixture was stirred at 100° C.for 24 hours.

Salt was eliminated by filtration, and the solvent was distilled offunder reduced pressure to thereby obtain 38.94 g of a crude product as ayellow liquid. The crude product was purified by distillation at reducedpressure (33 Pa, 97-101° C.), and 13.31 g of a desired product,3-pyrrolidinyl-1-2,2-triethylpiperidine (compound 1-II-12, yield of70%), was obtained as a colorless transparent liquid.

¹H NMR (400 MHz, CDCl₃, ppm): σ 0.82-0.89 (6H), 0.95-0.99 (3H),1.33-1.68 (10H), 1.76-1.95 (2H), 2.06-2.14 (1H), 2.28-2.34 (1H),2.51-2.57 (2H), 2.62-2.70 (4H), 2.74-2.82 (1H) ¹³C NMR (400 MHz, CDCl₃,ppm): σ 63.63, 60.47, 50.76, 44.79, 43.74, 26.14, 23.76, 23.34, 20.90,20.75, 15.05, 10.03, 7.31

Production Example 3 3-dimethylamino-1,2,2-triethylpiperidine (compound1-II-16)

N-Alkylation Step

A four-necked pear-shaped flask (500 mL) was charged with 10.02 g (0.054mol) of 3-amino-1,2,2-triethylpiperidine obtained in Example 1, 43.84 g(0.540 mol) of a 37% aqueous formaldehyde solution, and 24.89 g (0.541mol) of formic acid, and the mixture was stirred at 80° C. for 9 hours.

While cooling with ice, 100 g of a 48% aqueous sodium hydroxide solutionwas added thereto and extracted with chloroform (100 mL×3). The organiclayer was dried over sodium sulfate anhydride, and the solvent wasdistilled off under reduced pressure to thereby obtain 11.78 g of acrude product as a yellow liquid. The crude product was purified bydistillation at reduced pressure (20 Pa, 58-59° C.), and 6.98 g of adesired product, 3-dimethylamino-1,2,2-triethylpiperidine (compound1-II-16, yield of 61%), was obtained as a colorless transparent liquid.

¹H NMR (400 MHz, CDCl₃, ppm): σ 0.81-0.86 (3H), 0.88-0.91 (3H),0.95-0.98 (3H), 1.33-1.70 (6H), 1.77-1.95 (2H), 2.06-2.18 (1H), 2.22(6H), 2.28-2.35 (1H), 2.41-2.45 (1H), 2.62-2.65 (1H), 2.71-2.80 (1H) ¹³CNMR (400 MHz, CDCl₃, ppm): σ 64.18, 63.72, 44.84, 44.02, 43.77, 26.15,23.28, 20.87, 19.49, 15.11, 10.00, 7.51

Production Example 4 3-dimethylamino-1,2,2-triethylpiperidine (compound1-II-16)

Amination Step

A four-necked pear-shaped flask (500 mL) was charged with 14.04 g (0.07mol) of 2-(1-chloro-1-ethylpropyl)methyl-1-ethylpyrrolidine, 54.26 g(0.48 mol) of a 40% aqueous dimethylamine solution, and 100 mL ofethanol, and the mixture was stirred at 40° C. for 44 hours.

After extracting with chloroform (100 ml×3), the organic layer was driedover sodium sulfate anhydride, and then the solvent was distilled offunder reduced pressure to thereby obtain 9.35 g of a crude product as ayellow liquid. The obtained crude product was purified by silica gelchromatography (n-hexane:ethyl acetate=8:1) and 4.16 g (compound1-II-16, yield of 28%) of a desired product,3-dimethylamino-1,2,2-triethylpiperidine, was thus obtained as acolorless transparent liquid.

Reference Examples 1 to 3

Solutions shown in the following tables were prepared in a glasscontainer using synthesized melanin (made by Sigma-Aldrich Co.), andlight absorption (600 nm) after 30 minutes was measured by aspectrometer (U-3300, manufactured by Hitachi, Ltd.) to finddecomposition ratios (bleaching ratio) of the synthesized melanin. Thedecomposition ratio of the synthesized melanin was favorable when anycompound obtained in Production Examples 1 to 3 was used, as comparedwith Comparative Reference Example 1.

TABLE 1 Com- parative Reference Reference Reference Reference (g)Example 1 Example 2 Example 3 Example 1 0.1 mass % synthesized 0.5 0.50.5 0.5 melanin solution 5 mass % aqueous 0.5 0.5 0.5 0.5 monoethanolamine solution 15 mass % aqueous 0.5 0.5 0.5 0.5 hydrogen peroxidesolution Nonionic ion surfactant 0.5 0.5 0.5 0.5 (1.4 mass % aqueoussolution, SOFTANOL made by NIPPON SHOKUBAI CO., LTD.) 1 mass % aqueous0.5 0.5 0.5 0.5 EDTA/4Na solution 0.5 mass % aqueous 0.5 solution ofcompound 1-II-13 0.5 mass % aqueous 0.5 solution of compound 1-II-12 0.5mass % aqueous 0.5 solution of compound 1-II-16 Purified water 2   2  2   2.5 Total 5   5   5   5   Melanin bleaching ratio 81.6  78.3  75.8 70.3  (%)

Example 1 and Comparative Examples 1 to 3

The first part shown in Table 2 and the second part shown in Table 3were prepared, and when these agents were used in combination, bleachingproperties and the feeling to the touch were evaluated.

TABLE 2 Example product Comparative product First part (wt %) A B CCompound 1-II-12 1.7 — — Compound X — — 1.3 Ammonia (28 wt %) 7.5 7.57.5 EDTA-4Na 0.1 0.1 0.1 Propylene glycol 4   4   4   Stearyl trimoniumchloride 5   5   5   CETETH-40 2.5 2.5 2.5 Stearyl alcohol 8   8   8  Ammonium chloride 0.5 0.5 0.5 Purified water Balance Balance Balance pH10.2  10.2  10.2  Total 100    100    100   

TABLE 3 Second part (wt %) A B Hydrogen peroxide 17 23.7 (35 wt %)Methylparaben 0.1 0.1 Phosphoric acid Amount for adjusting pH Amount foradjusting pH to 3.5 to 3.5 Purified water Balance Balance Total 100 100(Treatment Method)

The first part and the second part were mixed in a mixing ratio (thefirst part:second part) shown in Table 4, and the resultant was appliedto a tress of black hair in a bath ratio (agent:hair)=1:1. After leavingat 30° C. for 30 minutes, the hair tress was rinsed with water at 40°C., washed with a commercially available shampoo and rinsed with water,and a commercially available conditioner was applied, and the hair tresswas then rinsed with water, wiped with a towel and dried.

[Evaluation of Bleaching Properties]

Brightness of a tress of hair bleached in accordance with the presentbleaching steps was measured by the CIE color specification system (L*,a*, b*) using a color-difference meter (color-difference meter CR-400manufactured by Konica Minolta Sensing, Inc.) and Δb* was calculatedaccording to the following formula. The larger Δb* indicated, the moreexcellent the bleaching properties are. Results are shown in Table 4.Δb*=b* ₂ −b* ₁(b*₁ denotes a b* value before bleaching and b*₂ demotes a b* valueafter bleaching)[Evaluation of the Feeling to the Touch]

Fingers were through in the hair tress bleached in accordance with thepresent bleaching steps, and the feeling of catching fingers, friction,and roughness were scored according to the following criterion so as toevaluate the feeling to the touch. Results are shown in Table 4.

A: There is a little feeling of catching fingers, but no feelings offriction and roughness.

B: There is a little feeling of catching fingers, and there are alsofeelings of friction and roughness.

C: There are feelings of catching fingers, friction and roughness.

TABLE 4 Example Comparative Example 1 1 2 3 First part A B C C (mixingratio) (1.0) (1.0) (1.0) (1.0) Second part A A A B (mixing ratio) (1.5)(1.5) (1.5) (1.5) pH (during mixing) 9.6 9.8 9.7 9.5 Bleachingproperties (Δb*) 7.3 5.2 5.6 7.3 Evaluation score of feeling A A A C tothe touch

According to Table 4, Example 1 in which a nitrogen-containing compoundof a component (a) is used is excellent with respect that both ofbleaching properties and feeling to the touch are preferable.Comparative Example 1 in which a nitrogen-containing compound is notused as the first part and Comparative Example 2 in which anitrogen-containing compound different from the component (a) is usedwere both inferior in bleaching properties. Comparative Example 3 inwhich an amount of hydrogen peroxide of the second part is increased soas to have equivalent bleaching properties to Example 1 had a poor scorein the feeling to the touch.

Example 2 and Comparative Example 4

The first part shown in Table 5 was prepared and evaluation of dyeingproperties was performed.

[Evaluation of Dyeing Properties]

The first part shown in Table 5 and the second part A shown in Table 3were respectively mixed in a mixing ratio of 1:1.5 (pH is 9.8 uponmixing), and the resultant was applied to a tress of white hair in abath ratio (agent:hair)=1:1. After leaving at 30° C. for 50 minutes, thehair tress was rinsed with water at 40° C., washed with a commerciallyavailable shampoo and rinsed with water, and a commercially availableconditioner was applied, and the hair was then rinsed with water, wipedwith a towel and dried.

A color tone of the hair tress dyed in accordance with the present hairdyeing steps was measured by the CIE color specification system (L*, a*,b*) using a color-difference meter (color-difference meter CR-400manufactured by Konica Minolta Sensing, Inc.) and ΔE* was calculatedaccording to the following formula. A larger ΔE* indicates moreexcellent dyeing properties. Results are shown in Table 5.ΔE*=√{square root over ((L* ₂ −L* ₁)²+(a* ₂ −a* ₁)²+(b* ₂ −b*₁)²)}{square root over ((L* ₂ −L* ₁)²+(a* ₂ −a* ₁)²+(b* ₂ −b*₁)²)}{square root over ((L* ₂ −L* ₁)²+(a* ₂ −a* ₁)²+(b* ₂ −b*₁)²)}  [Mathematical Formula 1](L*₁, a*₁ and b*₁ denote measured values before dyeing, and L*₂, a*₂ andb*₂ denote measured values after dyeing)

TABLE 5 Example Comparative Example First part (wt %) 2 4 Compound1-II-12 1 — Compound X — 1 Paraamino phenol 0.4 0.4Paraamino-ortho-cresol 0.5 0.5 Ammonia (28 wt %) 7.5 7.5 Propyleneglycol 4 4 Stearyl trimonium chloride 5 5 CETETH-40 2.5 2.5 Stearylalcohol 8 8 Amodimethicone*¹ 3 3 Sodium sulfite 0.5 0.5 Ascorbic acid0.5 0.5 Ammonium chloride*² q.s. q.s. EDTA-4Na 0.1 0.1 Purified waterBalance Balance Total 100 100 *¹SM8704C, Dow Corning Toray Co., Ltd.*²amount for adjusting pH to 10

TABLE 6 Comparative Example Example 2 4 L* 49.5 55.1 a* 25.2 21.8 b*36.6 35.5 Dyeing properties (ΔE*) 36 30

Example 2 is excellent with respect to showing preferable dyeingproperties according to a ΔE* value shown in Table 6, as compared withthe comparative example (Comparative Example 4) in which the formulationis common except for a nitrogen-containing compound.

Formulation Examples

Formulation examples of the first part are shown in Tables 7 and 8.These are used by combining with the second part that is generally used(pH is 9.9 when mixed with the second part A in a weight ratio of 1:1).

TABLE 7 Formulation Examples First part (wt %) 1 2 3 4 Compound 1-II-1 1— — — Compound 1-II-13 — 0.75 0.5 — Compound 1-II-12 — — 0.5 — Compound1-II-16 — — — 3 Paraamino phenol 0.3 0.1 — 0.1 2-hydroxyethyl-p- 0.1 —0.2 — phenylenediamine sulfate Toluene-2,5-diamine sulfate 0.2 — 0.3 —5-amino-ortho-cresol 0.1 0.1 — — Metaamino phenol 0.2 — 0.3 0.1 HC blue2 — 0.5 — — Basic yellow 57 — — 0.1 0.1 Red No. 106 0.1 — — — Stearylalcohol 8 8 8 8 COCAMIDE DEA 4.5 4.5 4.5 4.5 Glyceryl stearate (SE) 1.31.3 1.3 1.3 CETEARETH-30 4 4 4 4 Sodium lauryl sulfate 1 1 1 1 Oleicacid 2 2 2 2 Propylene glycol 1.5 1.5 1.5 1.5 PEG-9 dimethicone*³ 1.5 —1.5 1.5 Hydrolyzed keratin 0.5 0.5 0.5 0.5 Panthenol 0.8 0.8 0.8 0.8Ammonia (28 wt %) 6 3 1 — Ethanolamine — 3 4 5 EDTA-4Na 0.5 0.5 0.5 0.5Ammonium chloride*⁴ q.s. q.s. q.s. q.s. Purified water Balance BalanceBalance Balance Total 100 100 100 100 *³KF-6005, Shin-Etsu Chemical Co.,Ltd. *⁴Amount for adjusting pH to 10

TABLE 8 Formulation Examples (wt %) 5 6 7 8 9 Compound 1-II-12 0.5 — — —— Compound 1-II-1 0.5 2 — — — Compound 1-I-1 — — 1.5 — — Compound 1-I-2— — — 0.5 — Compound 1-I-11 — — — — 0.8 Toluene-2,5-diamine 0.1 0.1 0.2— 0.4 sulfate 5-amino-ortho-cresol 0.1 0.1 0.2 — 0.2 HC blue 2 0.05 — —0.08 0.03 Basic yellow 57 0.05 — 0.1 0.1 — Red No. 106 — 0.1 0.1 — —Ethanol 10 10 10 10 10 Propylene glycol 10 10 10 10 10 Oleic acid 10 1010 10 10 Oleamide DEA 8 8 8 8 8 Oleyl alcohol 2 2 2 2 2 CETETH-20 10 1010 10 10 PEG-9 dimethicone*⁵ 1.5 1.5 1.5 1.5 1.5 Ammonia (28 wt %) 8 3 33 3 Ethanolamine — 3 3 3 3 EDTA-4Na 0.1 0.1 0.1 0.1 0.1 Ammoniumchloride*⁶ q.s q.s q.s q.s q.s Purified water Balance Balance BalanceBalance Balance Total 100 100 100 100 100 *⁵KF-6005, Shin-Etsu ChemicalCo., Ltd. *⁶Amount for adjusting pH to 10

1. A hair dyeing composition, comprising a first part comprising a component (a) and a second part comprising a component (b), wherein a pH upon use is 7.5 to 12: (a) a nitrogen-containing compound expressed by the following general formula (1) or a salt thereof:

wherein n denotes an integer of 1 or 2, each of R¹ and R³ to R⁵ independently represents a hydrogen atom, a hydroxy group, or an alkyl group, an alkenyl group, an alkynyl group, a cyclic hydrocarbon group, an aralkyl group or a cyanated alkyl group each having 12 or less carbon atoms, or a 5 to 7 membered-ring saturated or unsaturated heterocyclic group, two of R² may be the same or different, and each represents a hydroxy group, —R or —OR, wherein R represents an alkyl group, an alkenyl group, an alkynyl group, a cyclic hydrocarbon group, an aralkyl group or a cyanated alkyl group each having 12 or less carbon atoms, or a 5 to 7 membered-ring saturated or unsaturated heterocyclic group, wherein R¹ to R⁵ may further have one or more substituents selected from the group consisting of a hydroxy group, an amino group, an alkyl group, a cyclic hydrocarbon group, an aralkyl group, a heteroaryl group, an alkoxy group, an ester group, and a cyanated alkyl group each having 8 or less carbon atoms, and wherein two or more of R¹ to R⁵ may be taken together to form a saturated or unsaturated 3 to 8 membered-ring, and the ring may have a substituent selected from the group consisting of a hydroxy group, and an alkyl group and a cyclic hydrocarbon group which have 12 or less carbon atoms and optionally may have a substituent; and (b) an oxidizing agent.
 2. The hair dyeing composition according to claim 1, wherein, in the general formula (1), R¹ represents a hydrogen atom, or an alkyl group or a cyclic hydrocarbon group each having 12 or less carbon atoms, two of R² may be the same or different alkyl group or cyclic hydrocarbon group each having 12 or less of carbon atoms, R³ and R⁴ each independently represents a hydrogen atom, or an alkyl group or a cyclic hydrocarbon group each having 12 or less carbon atoms, or the both may be taken together to form a nitrogen-containing saturated 5 or 6 membered-ring, and R⁵ represents a hydrogen atom, a hydroxy group, or an alkyl group or a cyclic hydrocarbon group each having 12 or less carbon atoms.
 3. The hair dyeing composition according to claim 1 or 2, wherein the first part comprises an oxidative dye intermediate.
 4. The hair dyeing composition according to claim 1, wherein the first part comprises a direct dye.
 5. A method of hair dyeing, comprising the steps of: mixing the first part and the second part of the hair dyeing composition according to claim 1 immediately before use; applying a mixture of the first part and a second part to the hair; and leaving the hair for 1 to 60 minutes, and then rinsing the hair. 